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United States Patent '2 NEW COLOURATION PROCESS FOR TEXTILE MATERIALS Claims priority, application Great Britain April 10, 1957 3 Claims. (Cl. 8-65) The invention relates to a new colouration process for textile materials and more particularly to a new colouration process for producing patterned effects on textile materials by resist printing.

It is known that white resist patterns can be obtained on cellulosic textile materials by printing the textile materials with a resist paste containing sodium formaldehyde sulphoxylate and dirnethylphenylbenzylammonium chloride, drying, and then padding the textile materials with a solution of a reactive dyestufi, for example an azo or anthraquinone dyestutf containing a dichloro-triazinyl radical, and finally heating to fix the dyestutf. This process has the disadvantage that the resist paste is unstable when it is exposed to atmospheric oxidation, the outlines of the resisted portions are not always well-defined, and slight discolouration of the ground shade is sometimes produced. Furthermore when a coloured resist using a vat dyestulf is printed alongside a white resist, the colour yield from the vat dyestuif is appreciably reduced where the vat dyestuil paste comes into contact with the white resist paste.

We have now found that organic amino compounds can be used to give effective resists under reactive dyestuffs and that the disadvantages of the known resist printing process can be avoided by using resist pastes containing organic amino compounds.

According to our invention we provide a new colouration process for textile materials which comprises locally applying to the textile materials a resist paste comprising an organic amino compound and a thickening agent, and subsequently padding the textile materials with a solution of a reactive dyestufr' as hereinafter defined, and when the textile material is of natural or regenerated cellulose, an alkaline compound or a compound which on heating or steaming gives rise to an alkaline compound.

By a reactive dyestuff we mean a dyestufi containing a reactive halogen atom or other reactive atom or group, that is to say a halogen atom or other group capable of reacting with the fibre. Usually, reactive dyestufis are water-soluble. They are principally used for vegetable fibres and regenerated cellulose, also using an alkali treatment to cause reaction therewith, and preferably have a small afiinity for these materials when applied under conditions other than those giving rise to reaction with the material, so that unreacted dyestuff may readily be washed from the material after the colouration process. Examples of classes of such reactive dyestuffs include dyestuffs containing a =s-triazinyl radical carrying one or two chlorine or bromine atoms directly attached to the triazine ring, dyestufis containing'a pyrimidyl radical carrying one or two chlorine or bromine atoms directly attached to the pyrimidine ring, and dyestufifs containing a beta halogenopropionyl, betahalogenoethylsulphonyl, beta halogenoethylsulphamyl, beta-sulphatoethylsulphonyl, beta-hydroxyethylsulphonyl, chloroacetylamino, beta (chloromethyl)-beta-sulphatoethylsulphamyl, alkyl phosphite, or sulphon fluoride radi- Patented July 21, 1959 ice cal. The dyestuffs in these classes may be for example nitro dyestuffs or dyestufis of the azo, anthraquinone or phthalocyanine series and may be metal free or may contain metal in complex formation. Specific examples of suitable dyestuifs are described in United Kingdom specification No. 209,723 in Examples 1 and 2, United Kingdom specification No. 298,484 in Example 1, in United Kingdom specification Nos. 460,224, 733,471, 740,533, 775,308, 772,030, 774,925, 780,591, 781,930, 785,120, 785,222 and in German Auslegeschrift No. 1,008,313.

The organic amino compounds should preferably be soluble in water. They may contain substituted or unsubstituted amino groups and may be for example monoamines such as diethylamine, diamines such as ethylene diamine, polyamines such as diethylene triamine, triethyl ene tetramine, tetraethylene pentamine, acid amides such as formamide or dimethylformamide, amino-alcohols such as mono-, di-, and tri-ethanolamine and beta-diethylaminoethanol and cyclic amino compounds such as hexamethylene tetramine and polyvinylpyrrolidone. It is preferred however to use as the amino compound, an aminoacid for example glycine, benzylglycine, phenylglycine, phenylglycine-o-carboxylic acid, methyltaurine, N-methyl-, N-ethyland N-benzylanthranilic acid, N-benzyl'sulphoanthranilic acid, 2-ethylamin0-5-sulphobenzoic acid and especially, sarcosine. The amino acid may be used in the form of a water-soluble salt, for example an alkali metal salt.

The quantity of organic amino compound required will depend on the nature of the organic amino compound used and also on the thickening agent and dyestufi used but in general it is found that between 2% and 10% of organic amino compound calculated on the weight of the resist paste gives satisfactory results in practice. Quantities outside these limits may be used if desired, provided that there is a molecular excess of the amino compound, preferably at least 5 molecular proportions, relative to the amount of dyestufi present.

As a suitable thickening agent for use in the resist paste there may be mentioned, for example, British gum thickemng.

The textile materials which may be coloured by the process of our invention include not only cellulosic materials such as cotton and viscose but also protein materials such as silk and wool and textile materials made from artificial fibres such as nylon.

The resist paste may be prepared by mixing the thickening agent with the organic amino compound, preferably in aqueous solution, and the paste may be applied to the textile material by, for example, stencil, block, screen or machine printing processes. If desired other resists, for example vat dyestufi coloured resists, may also be applied. The dyestulf solution may then be applied by padding. The alkaline compound for example sodium" carbonate or the compound which on heating or'steam' ing gives rise to an alkaline compound, for example sodium bicarbonate, is conveniently added to the dyestuif soltuion but, if desired, it may be applied to the textile material before or after padding with the dyestutf solu tion. After application of the dyestufi solution and the alkaline compound, or compound which on heating or steaming gives rise to an alkaline compound, the textile material may be steamed, or heated for example in a hot air chamber or on steam-heated drying cylinders to fix the dyestuff. The textile material may then be rinsed in cold Water and finally treated in a hot dilute aqueous solution of a detergent, for example, a sulphated fatty alcohol or a condensation product of alkylphenols with ethylene oxide, and finally rinsed in water and dried.

By the process of the invention good clear white resists with sharp outlines are obtained and there is no appreci- Example 1 Cotton cloth is printed with a resist paste made up by mixing together 70 parts of British gum thickening and 30 parts of a 13.4% aqueous solution of the sodium salt of sarcosine. The cloth is dried and then padded through a dyestuff solution prepared by dissolving 2 parts of the dyestuff described in Example 3 of Belgian specification No. 543,214 in 87 parts of water and adding parts of 5% sodium alginate thickening and then 1 part of sodium bicarbonate. The cloth is dried in a hot flue and steamed for 5 minutes in a conventional ager, rinsed well in cold water and then treated for 5 minutes in a bath containing 1 part of a detergent mixture, consisting of alkylphenols condensed with ethylene oxide and a sulphated fatty alcohol, in 1000 parts 'water at between 85 and 100 C. The cloth is finally rinsed in cold water and dried.

The portions printed with the resist paste prevent the fixation of the dyestuff and a good clear white pattern on a brilliant red background is obtained.

In the above example, instead of fixing the dyestufr' on the padded cloth by drying and then steaming, the dyestuff may be fixed by passing the cloth over steam-heated cylinders or by heating in a hot air dryer.

In place of the 2 parts of dyestufi used in the above example, there may be used 2 parts of the dyestuff described in Example 1 of Belgian specification No. 543,215 or 2 parts of the dyestufl described in Example 1 of Belgian specification No. 543,216 when a white pattern on a yellow ground and a white pattern on a blue ground respectively are obtained.

Example 2 In place of the resist paste used in Example 1, there Example 3 In place of the resist paste used in Example 1 there may be used resist paste made up by mixing together 70 parts of British gum thickening, 5 parts of 2-ethylamino-5- sulphobenzoic acid and 25 parts of water when a similar result is obtained.

Example 4 In place of the resist paste used in Example 1 there may be used a resist paste made up by mixing 70 parts of British gum thickening, 10 parts of hexamethylenetetramine and 20 parts of water when a similar result is obtained.

Example 5 A cloth made from polyamide fibre is printed with a resist paste made up by mixing 70 parts of British gum thickening and 30 parts of a 13.4% aqueous solution of the odium salt of sarcosine. The printed cloth is dried and padded in a dyestufi solution made up by dissolving 0.5 part of the dyestutf described in Example 1 of Belgian specification No. 543,214, 3 parts of urea, 1 part of ammonium oxalate an 10 parts of a 5% sodium alginate thickening in 85.5 parts of water.

The cloth is dried on steam heated drying cylinders, steamed for 5 minutes in a conventional steamer, rinsed well in cold water and then treated for 5 minutes at 85 C. in a Solution of 2 parts of a detergent mixture, consisting of alkylphenols condensed with ethylene oxide and a alcohol, and 2 parts of soda ash in 1000 sulphated fatty The cloth is rinsed in cold water and parts of water. dried.

The portions printed with the resist paste prevent the fixation of dyestuif and a good clear white pattern on a brilliant red background is obtained.

Example 6 Cloth made from natural silk is printed with a resist paste prepared as described in Example 5. The cloth is dried and padded with a dyestufi solution made by dissolving 0.5 part of the dyestuff described in Example 1 of Belgian specification No. 543,215 in 88.5 parts of water and adding 10 parts of 5% sodium alginate thickening and 1 part of sodium bicarbonate. The fabric is dried in a hot air chamber, steamed for 5 minutes, rinsed well in cold water and then treated for 5 minutes at 40 C. in a solution of 2 parts of the detergent mixture used in Example 1 in 1000 parts of water. The cloth is rinsed in cold water, and dried.

The portions printed with the resist paste prevent the fixation of dyestufi and a good clear white pattern on a blue background is obtained.

Example 7 In place of the dyestuif solution used in Example 1 there is used a dyestuff solution made by dissolving 1 part of the blue disazo dyestufi shown in the first formula on page 586 of The Chemistry of Synthetic Dyes, volume 1, by K. Venkataraman (New York Academic Press, 1952), and 5 parts of urea in 83 parts of water and adding 10 parts of 5% sodium alginate thickening and 1 part of sodium bicarbonate.

The areas printed with the resist paste prevent the fixation of dyestuff and a good clear white pattern is produced on a greenish-blue ground.

Example 8 In place of the dyestufi solution used in Example 1 there is used a dyestuff solution made by dissolving 0.5 part of the dyestufi prepared as described below and 10 parts of urea in 79.5 parts of water and adding 10 parts of a 5% sodium alginate thickening and 1 part of sodium bicarbonate. The fixation of the dyestutf is carried out by the steaming process.

The areas printed with the resist paste prevent the fixation of the dyestufi and a white patterned eifect is produced on a turquoise blue ground.

The dyestufi used in this example may be made by treating 50 parts of the sodium salt of copper phthalocyaninetetra-4-sulphonic acid with 475 parts of chlorosulphonic acid at C. for 4 hours, pouring the mixture onto ice and treating the precipitated sulphonchloride with a solution of 12.8 parts of 2-chloroethylamine hydrochloride in aqueous sodium bicarbonate when the sulphonchloride groups are in part replaced by sulphon: fi-chloroethylamide groups and in part hydrolysed to sulphonic acid groups.

Example 9 1 In place of the 30 parts of a 13.4% aqueous solution of the sodium salt of sarcosine used in Example 1 there may be used 30 parts of 16.7% solution of diethylamine, ethylene diamine, benzylglycine, N-ethylanthranilic acid, Z-ethylamino-S-sulphobenzoic acid, N-methylglucosamine, or polyvinylpyrrolidone or a 33% solution of hexamethylenetetramine or tetraethylene pentamine or a 7% solution of glycine or methyltaurine when similar results are obtained.

Example 10 Cotton cloth is machine printed with a copper roller using a resist paste made up. by mixing together 70 parts of British gum thickening and 30 parts of a 13.4% aqueous solution of the sodium salt of sarcosine. The cloth is then printed in a different pattern with a second copper roller using a vat printing ,paste made up by mixing 6 parts of Caledon Printing Jade Green XBNS (the dyestufi C.I. Vat Green 1 .of the Colour .Index, 1957 edition, volume II), 75 parts British gum thickening, 6 parts of sodium carbonate, 5 parts of glycerol, 8 parts of sodium formaldehyde sulphoxylate.

The cloth is then dried and padded through the dye stuff solution used in Example 1, steamed for 5 minutes, rinsed in cold water, treated for 2 minutes in a cold 5 and 0.2% acetic acid, rinsed again and treated for 5 minutes in a boiling'aqueous solution containing 0.3% of the detergent mixture used in Example 1, rinsed in cold water, and finally dried. White and green patterned effects on a brilliant red background are obtained.

The following table describes in the first column further examples of dyestuffs which may be substituted in Example 1 for the dyestutf used therein; in each case there is obtained "a good clear White pattern on a backaqueous solution containing 0.2% sodium dichromate 1 ground of the colour indicated inthe second column.

GHaGONH OH (I) NHQ ii NH N= Do.

/CHg

Greenish-blue.

Dyestufl Colour (I) N H3 S OaNa Reddish blue.

O NH:

I l S0 Na ?r Greenish-blue.

II i l? NaOaS O NH NH-C G-Br S O Na The dyestuil obtained by treating 115 parts of copper pythalocyanine with 1,200 parts of chlorosulphonic acid at 138 C. for 4 hours, pouring the mixture on to ice and treating the precipitated sulphonchloride with a solution of 60 parts of 3-chloro'2-hydroXypropyl- Tut uoiseblue amine hydrochloride in aqueous sodium bicarbonate, when the sulphonchloride groups q are in part replaced by 3-chloro-2-hydroxypropylsulphamyl groups and in part by sulphonic acid groups.

pound which on being subjected to an elevated temperature gives rise to an alkaline compound.

2. Process as claimed in claim 1 wherein the organic What we claim is: l 30 1. New colouration process for textile materials, selectcd from the group consisting of cotton, viscose, silk,

wool, and nylon, which comprises locally applying to amine compound usedis sarcosine.

the textile materials a resist paste comprising an organic 3. Process as claimed in claim 1 wherein the resist amino compound, selected from the group consisting of 3 paste contains between 2% and 10% by weight of the amino acids, amino alcohols, saturated cyclic amines, organic amino compound.

and aliphatic monoand polyamines, and a thickening agent, and subsequently padding the textile materials e e ences Cited in the file of this patent with a solution of a reactive dyestufi having a reactive group capable of reacting with the fiber, and, when the 40 UNITED STATES PATENTS textile material is of cellulose, a member selected from 1,913,410 Rivat June 13, 1933 the group consisting of an alkaline compound and a com- 2,726,133 Helfenberger Dec. 6, 1955 

1. NEW COLOURATION PROCESS FOR TEXTILE MATERIALS, SELECTED FROM THE GROUP CONSISTING OF COTTON, VISCOSE, SILK, WOOL, AND NYLON, WHICH COMPRISE LOCALLY APPLYING TO THE TEXTILE MATERIALS A RESIST PASTE COMPRISING AN ORGANIC AMINO COMPOUND, SELECTED FROM THE GROUP CONSISTING OF AMINO ACIDS, AMINO ALCOHOLS, SATURATED CYCLIC AMINES, AND ALIPHATIC MONO- AND POLYAMINES, AND A THICKENING AGENT, AND SUBSEQUENTLY PADDING THE TEXTILE MATERIALS WITH A SOLUTION OF A REACTIVE DYESTUFF HAVING A REACTIVE GROUP CAPABLE OF REACTING WITH THE FIBER, AND WHEN THE TEXTILE MATERIAL IS OF CELLULOSE, A MEMBER SELECTED FROM THE GROUP CONSISTING OF AN ALKALINE COMPOUND AND A COMPOUND WHICH ON BEING SUBJECTED TO AN ELEVATED TEMPERATURE GIVES RISE TO AN ALKALINE COMPOUND. 